The effect of substrate temperature on the oxidation behavior of erbium thick films

The effect of substrate temperature on the oxidation behavior of erbium thick films, fabricated by electron-beam vapor deposition (EBVD), was investigated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The erbium thick film is black when it is deposited at substrate temperature below 450 °C and turns gray at higher substrate temperature in a vacuum pressure of approximately 1.5 × 10⁻⁶ Torr, which indicates that the thickness of erbium oxide layer formed on the surface of erbium films increases with the decreasing substrate temperature. XPS depth profile results demonstrate that the thickness of the surface erbium oxide layer of erbium film deposited at substrate temperature of 550 and 350 °C are about 50 and 75 nm, respectively. The thicker oxide layer at lower substrate temperatures may be attributed to grain size and the dynamic vacuum condition around the substrates. Other possible factors involved in the oxidation behavior are also discussed.     

X-ray photoelectron spectroscopy and thermal desorption spectroscopy comparative studies of L-CVD SnO2 ultra thin films

In this paper we present the results of comparative studies of the chemical stability of L-CVD SnO₂ ultra thin films (20 nm) deposited on the atomically clean Si(100) substrate after their subsequent in situ hydrogenation and oxidation, and then after air exposure. For the control of surface chemistry of these films we used in a comparative way the X-ray Photoemission Spectroscopy (XPS) combined with ion depth profiling (DP XPS) and Thermal Desorption Spectroscopy (TDS). Our XPS experiments showed that the L-CVD SnO₂ ultrathin films after subsequent in situ hydrogenation and oxidation consist of strongly nonstoichiometric layer at the top of Si dioxide substrate. After subsequent air exposure they were covered with undesired 3 monolayers of C contamination and various forms of oxygen. During the TDS procedure a two-step desorption of molecular hydrogen (H₂), water vapor (H₂O), carbon dioxide (CO₂) and atomic oxygen (O) at the temperatures of ~ 530 K and 600 K was observed, respectively. The TDS results were in a good correlation with evident decreasing of the relative concentration of C contaminations, as well as variation of nonstoichiometry of the L-CVD SnO₂ ultra thin films as determined by XPS combined with ion depth profiling.     

MlNi_4Co_(0.6)Al_(0.4)储H_2合金表面吸H_2的TDS研究

用热脱附谱 (TDS)对不同表面处理的富La混合储H2 合金MlNi4 Co0 6Al0 4 粉末样品进行H2 气吸附和脱附特性的比较和研究。未经表面处理的粉末样品 ,只测到一个H2 脱附峰 (α峰 ) ,脱附温度在 40 0K左右 ;经 6molKOH溶液 ,在 80℃下处理 6h的MlNi4 Co0 6Al0 4 粉末样品 ,有 2个H2 热脱附峰 (β峰和γ峰 ) ,脱附温度分别在 5 40和 6 30K处 ;而用 6molKOH 0 0 2molKBH4 溶液处理后 ,则有 3个H2 热脱附峰 (α峰 ,β峰和γ峰 ) ,脱附温度分别在 40 0 ,5 30和 6 40K处。TDS研究表明 ,热碱加还原的处理使材料表面对H2 气吸附的活性和容量提高 ,并使各个吸附态的扩散和转变更加容易。     

Post deposition annealing of aluminum oxide deposited by atomic layer deposition using tris(diethylamino)aluminum and water vapor on Si(100)

Thin stoichiometric aluminum oxide films were deposited using tris(diethylamino)aluminum precursor and water. Changes in aluminum oxide film and interfacial regions were studied after post deposition annealing under inert ambience at 600, 800 and 1000 °C using Fourier Transform InfraRed (FTIR) spectroscopy, X-ray Photoelectron Spectroscopy, and Scanning Transmission Electron Microscopy (STEM)/Electron Energy Loss spectroscopy (EELS) techniques. STEM/EELS analyses were also done on samples annealed in situ, i.e., inside the electron microscope at temperatures as high as 800 °C. Up to an annealing temperature of 600 °C, the atomic layer deposited alumina film was thermally stable and remained amorphous with no interfacial silica growth observed. After annealing at 800 °C for 5 min, the only change observed was a small increase in the interfacial layer thickness which was found to be mainly silicon oxide without any significant silicate content. Annealing at 1000 °C induced a significant increase in the interfacial layer thickness which consisted of a mixture of silicon oxide and aluminum silicate. The composition of the interfacial layer was found to change with depth, with silicate concentration decreasing with distance from the Si substrate. Also, the FTIR spectra exhibited strong absorption features due to Al-O stretching in condensed AlO₆ octahedra which indicate crystallization of the alumina film after annealing at 1000 °C for 5 min.     

In-situ electrical characterization of ultrathin TiN films grown by reactive dc magnetron sputtering on SiO2

Ultrathin TiN films were grown by reactive dc magnetron sputtering on thermally oxidized Si (100) substrates. The electrical resistance of the films was monitored in-situ during growth in order to determine the minimum thickness of a continuous film. The coalescence thickness has a minimum of 1 nm at a growth temperature of 400 °C after which it increases with growth temperature. The minimum thickness of a continuous film decreases with increasing growth temperature from 2.9 nm at room temperature to 2.2 nm at 650 °C. In-situ resistivity measurements show that films grown at 500 °C and above are resistant to oxidation indicating high density. X-ray photoelectron spectroscopy and X-ray diffraction measurements show that the TiN grain stoichiometry and grain size increases with increasing growth temperature.     

XPS and TEM study of W-DLC/DLC double-layered film

A double-layered film of tungsten-containing diamond-like carbon (W-DLC) and DLC, (W-DLC)/DLC, was investigated. A film of 1.6 µm in thickness was deposited onto silicon substrate. The investigate double-layered coating was deposited by using the combination of PECVD and co-sputtering of tungsten metal target. Structure, interface and chemical bonding state of the investigated film were analyzed by Transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). From the results of the analyses, the structure of double-layered film is that amorphous phase of carbon is continued from DLC to W-DLC and tungsten metal clusters are dispersed in W-DLC layer.     

In-situ monitoring of the thermal desorption of alkanethiols with surface plasmon resonance spectroscopy (SPRS)

Thermal desorption investigations on self-assembled monolayers (SAMs) had previously been carried out using techniques such as thermal desorption spectroscopy (TDS), scanning tunneling microscopy (STM) and X-ray photo-electron spectroscopy (XPS). In this paper, the thermal dissociation of alkanethiols (CnH(2n + 1)SH) at various chain lengths (n= 6, 12, 18) on sputtered gold layers was monitored in-situ using the Kretschmann surface plasmon resonance configuration on a spectroscopic ellipsometer. We found that the longest alkanethiol (C18) exhibits the greatest thermal stability, manifested by the least amount of angular shift, during heating, in the resonant spectral features. Predictions of desorption temperatures from SPRS for the longer chain thiols are in good agreement with XPS measurements.     

Optical recording characteristics of molybdenum oxide films prepared by pulsed laser deposition method

Molybdenum-oxide (MoO₃)films were deposited on glass substrates (Corning #7059 with an area of 26 × 38 mm²) by pulsed laser deposition using an ArF excimer laser. It was found that after annealing at 340 °C for 10 min, the film thickness became 2.3 times that (approximately 30 nm) of the as-deposited film thickness. The difference in the transmittance, ΔT, between the annealed state and the as-deposited state was about 40% at a wavelength of 400 nm. X-ray diffraction spectra indicated that oxygen was absorbed into the MoO₃ films through the annealing process. From revolution testing of 30 nm-thick MoO₃ films without a protective layer deposited on a polycarbonate DVD-R disk substrate (120 mm?, 0.6 mm thickness), a write peak-power dependence of carrier-to-noise ratio (CNR) (recording on-land, at λ = 406 nm, NA = 0.65) of the 3T signal (58.5 MHz) was measured at a linear velocity of 5 m/s and a read power of 0.6 mW. Consequently, CNR near 50dB was obtained in the wide write-power margin ΔP of 7 mW (at peak powers between 3.5 and 10.5 mW). From SEM observations, it was recognized that bits of 0.25-0.30 μm size, corresponding to a storage capacity of 7-10GB/in² in the case of NA = 0.65, were formed. For the sample structure with an Al₂O₃ protective layer of ~ 20 nm thickness, a CNR near 50dB was obtained in the peak-power margin ΔP of 12 mW (at peak powers between 6.0 and 18.0 mW). Larger values of the CNR can be obtained if the film thickness of each layer including both the active and protective layers is optimized.     

Preparation and characterization of atomically flat and ordered silica films on a Pd(100) surface

Ultrathin silica films with different thicknesses have been grown on a Pd(100) surface by depositing silicon in the presence of O₂. The film composition and electronic properties were characterized by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and high-resolution electron energy loss spectroscopy (HREELS). Scanning tunneling microscopy was applied to investigate the film morphology and lattice structure. The results show that the obtained films are atomically flat and highly ordered in a long range. UPS and HREELS measurements indicate that the silica film has the same electronic and vibrational properties as bulk silica. A 2.8 nm thick film exhibits low defects in the film and high thermal stability up to 800 K, as evidenced by ion scattering spectroscopy and XPS.     

Study on adhesion and wear resistance of multi-element (AlCrTaTiZr)N coatings

Multi-element (AlCrTaTiZr)N films were deposited on cemented carbide and M2 steel substrates by reactive RF magnetron sputtering. Prior to nitride film deposition, an interlayer between the film and the substrate was introduced to improve adhesion property. The influence of interlayer materials (Ti, Cr, and AlCrTaTiZr alloy) and interlayer thickness (0–400 nm) on the adhesion and tribological properties of films was investigated. In this study, the nitride film deposited at R_N = 20% exhibited the highest hardness (35.2 GPa) and the lowest residual compressive stress (? 1.52 GPa), and was prepared as the top layer for further testing. The interlayer materials can effectively improved the film adhesion onto the cemented carbide substrates, and the adhesive failure was not observed even under the normal load of 100 N. For M2 steel substrates, only the Cr interlayer can slightly improve the film adhesion, and the cohesive and adhesive failure can be found at relatively lower applied load. The optimal interlayer thickness was 100–200 nm for the 1 µm-thick (AlCrTaTiZr)N film and can be related to the stress evolution. The friction coefficient and wear rate for the (AlCrTaTiZr)N film were 0.82 and 4.9 × 10^? 6 mm³/Nm, respectively, and almost kept constant under different interlayer materials and thickness. The worn-through event of the nitride film during tribological test occurred easily owing to its poor adhesion behavior, and can be improved by interlayer additions.     

Co-adsorption of CO and oxygen on W(110) surfaces

Influence of oxygen adsorption on CO chemisorption behavior over W(110) surfaces was studied using valence band spectra and thermal desorption spectroscopy (TDS). In the absence of O, CO formed a tilted and a vertical structure at 120 K on W(110). In the presence of O coadsorbate, in contrast, formation of the tilted structure of CO was suppressed. CO desorption from oxygen-covered W(110) surfaces showed indication of a strong interaction between adsorbates at ∼900 K, which was absent without O.     

Characterization of the protective surface films formed on molten magnesium in air/HFC-134a atmospheres

The surface films formed on molten magnesium in an air/HFC-134a gas mixture at 700 °C were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Auger electron spectroscopy (AES). The results showed that there was a protective film on molten magnesium surface, which can prevent molten magnesium from oxidation and ignition. The surface film contained primarily four elements: magnesium, fluorine, oxygen and carbon, and was composed of MgF₂, MgO and C. The film properties depended on the HFC-134a concentration in the gaseous mixture and exposure time. The thickness of the film formed after exposure to air containing 0.5% HFC-134a for 10 min was about 1–2 μm.     

The structure and composition of oxidized and reduced tungsten oxide thin films

The structure, morphology and composition of pure WO₃ thin films deposited onto vacuum-cleaved NaCl(001) single crystals have been studied at different substrate temperatures up to 580 K and under different oxidative and reductive treatments in the temperature range 373-873 K by Transmission Electron Microscopy, Selected-Area Electron Diffraction and X-ray Photoelectron Spectroscopy (XPS). A transition from an amorphous structure obtained after deposition at 298 K to a more porous structure with small crystallites at the highest substrate temperatures has been observed. XPS spectra reveal the presence of W⁶⁺ irrespective of the preparation procedure. Significant changes in the film structure were only observed after an oxidative treatment in 1 bar O₂ at 673 K, which induces crystallization of a monoclinic WO₃ structure. After raising the oxidation temperature to 773 K, the film shows additional reconstruction and a hexagonal WO₃ structure becomes predominant. This hexagonal structure persists at least up to 873 K oxidation temperature. However, these structural transformations observed upon oxidation were almost completely suppressed by mixing the WO₃ thin film with a second oxide, e.g. Ga₂O₃. Reduction of the WO₃ films in 1 bar H₂ at 723-773 K eventually induced the formation of the β-W metal structure, as evidenced by electron diffraction and XPS.     

Probing interfacial properties of ferromagnetic/insulator bilayers with X-ray spectroscopies: Application to Fe,Co, Mn/MgO(0 0 1) interfaces

Electronic and magnetic properties of bcc Co, Fe and Mn(0 0 1) epitaxial monolayers in contact with a single-crystalline MgO(0 0 1) film were studied using X-ray photoemission spectroscopy (XPS), X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements. The XPS and XAS analysis clearly evidenced the weak hybridization between the MgO barrier and Fe or Co. On the contrary, a net oxidization of the Mn layer in contact with the MgO layer was observed. The magnetic properties were characterized by probing the XMCD signal of a unique atomic plane of transition metal in contact with MgO. The total magnetic moment per Co and Fe atoms were observed to increase compared to the bulk at the metal/oxide interface. Finally, Mn at the interface with MgO does not present any ferromagnetic behavior. This was assumed to be a consequence of the Mn oxidization.     

Crystal structure and optical absorption investigations on β-In2S3 thin films

The crystal structure of annealed β-In₂S₃ thin films with different thickness was investigated by X-ray diffraction technique. Lattice parameters, crystallite size and microstrain were calculated. It was found that the lattice parameters are independent on film thickness, while annealing temperatures increase them. Crystallite sizes were increased with the increase of the film thickness and improved by annealing temperatures. In all cases, the microstrains were decreased gradually with the increase in both film thickness and annealing temperatures. Optical properties of β-In₂S₃ thin films were performed in the spectral range from 400 to 2500 nm to determine the optical constants (n and k), the high frequency dielectric constant, ε_∞, the lattice dielectric constant, ε_L, and the energy gap. The optical constants were found to be independent on film thickness in the range from 200 to 630 nm. The high frequency dielectric and lattice dielectric constants of the as-deposited film increased by annealing temperatures. The energy gap for the as-deposited In₂S₃ was found to be 2.60 eV and increased to 2.70 and 2.75 eV by annealing at 423 and 473 K for 1 h, respectively.     

Ultra-thin zinc oxide film on Mo(100)

Zinc oxide films on a single crystal Mo(100) substrate were fabricated by annealing the pre-deposited metal Zn films in 10^− 5-10^− 4 Pa O₂ ambience at 300-525 K, and were characterized by in situ Auger electron spectroscopy, electron energy loss spectroscopy, low energy electron diffraction and high-resolution electron energy loss spectroscopy. The results show that the atomic ratio of oxygen to zinc in zinc oxide film is significantly dependent on sample annealing temperature and O₂ pressure. A stoichiometric zinc oxide film has been obtained under ∼10^− 4 Pa O₂ at about 400 K. A redshift of Fuchs-Kliewer phonon energy correlated with surface oxygen deficiency is observed.     

Synthesis and optical characterization of n-ZnO and p-Cu2ZnSnS4 nanocrystalline thin films for low cost solar cells

High quality ZnO/Cu₂ZnSnS₄ thin films as a window/absorber layers were successfully synthesized via spin coating the sol-gel precursor of each composition without using any vacuum facilities. In this study, the impact of annealing temperature (400 °C, 3 h) on the ZnO window layer and different thickness (3 and 5 layers) of the Cu₂ZnSnS₄ (CZTS) absorber layer were investigated. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM) and UV–vis–NIR spectroscopy were used for the structural, compositional, morphological and optical absorption analysis of each layer. ZnO exhibits wurtzite hexagonal crystal structure with particle size equals to 8.60 and 28.59 nm for fresh and annealed films, respectively. Micro-strain and dislocations density decreased with the annealing temperature. X-ray diffraction patterns for CZTS films show small peak at (112) according to the kesterite structure with particle size in nano-scale for the two thicknesses. ZnO films demonstrated direct optical band gap of 3.23 and 3.21 eV for fresh and annealed films, respectively. CZTS films (3 and 5 layers) also have direct optical band with optimum value (1.51 eV) for thickness of 5 layers. The J-V characteristics of the CZTS-based thin film solar cells (CZTS/ZnO/ZnO:Ag) were measured under air mass AM 1.5 and 100 mW/cm² illumination. The values of the short circuit current (J_sc), open circuit voltage (V_oc) and fill factor (FF) also have been obtained.     

High-temperature growth and in-situ annealing of MgZnO thin films by RF sputtering

We report the effect of growth temperature and annealing on microstructural, elemental and emission properties of as-grown and in-situ annealed MgZnO thin films, containing ∼ 10 at. % Mg, grown at high temperature by RF sputtering. Microstructural analysis carried out by TEM reveals formation of thin oxide layer with increased layer thickness on growth temperature, in the interface between Si substrate and MgZnO thin film. Irrespective of growth temperature, increase in Mg mole fraction with increase in thickness of MgZnO thin film is observed from EDX and AES spectroscopy, and a maximum of 14 at. % Mg is observed at 800 °C. The photoluminescence investigation shows blue shift of 104 meV in MgZnO film grown at 800 °C, compared to the film grown at 600 °C, which is due to the enhancement of the Mg incorporation at higher temperature. In addition, annealing at the growth temperature enhanced the intensity ratio of the UV/deep level emission and increased the grain size. Thermal treatment in a vacuum improved the emission efficiency and changed the origin of the point defects.     

Surface characteristics of Ti6Al4V alloy: effect of materials, passivation and autoclaving

The properties of passivated films for Ti6Al4V alloy prepared by various methods (as-polished, brazed at 970 °C for 2 h and brazed at 970 °C for 8 h) were investigated. Four passivations (non-treated, nitric acid passivation, 400 °C-treated in air, and aged in boiling water), with or without autoclaving treatments, were adopted for evaluating the changes of surface properties, including chemical composition, chemical structure, and oxide thickness. From X-ray photoelectron spectroscopic (XPS) analyses, surface elements of copper and nickel in brazed samples were undetected for non-treated, acid-passivated and boiling water-aged specimens, while they were found in the 400 °C-treated specimen. The relative contents of Ti2++Ti3+ to Ti4+ were determined by passivation treatments, but were not related to the experimental materials and autoclaving treatment. Passivation and autoclaving decreased the Ti to Ti4+ ratio by virtue of an increase in oxide thickness. Of the four types of passivation treatment, the 400 °C thermal treatment exhibited the lowest content of suboxides and metallic elements and the thickest oxide by XPS analysis; however, this treatment may cause a desorption of the basic OH group in the hydration layer on the surface of titanium alloy.     

Room temperature plasma oxidation in DCSBD: A new method for preparation of silicon dioxide films at atmospheric pressure

In this paper a new process for the preparation of thin silicon dioxide (SiO₂) film is presented: the oxidation of c-Si (1 1 1) surface in atmospheric pressure plasma at room temperature. Diffuse coplanar surface barrier discharge (DCSBD) at atmospheric pressure in air and oxygen atmosphere has been used. The oxidation rate and the thickness of oxidized layers were estimated by ellipsometry. The structure and the chemical composition of oxidized layers were investigated by infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray (EDX) analysis. Scanning electron microscopy (SEM) was used to observe the morphology of the layer surface. It was found that stoichiometric SiO₂ layers were obtained with oxidation rates comparable to thermal oxidation.